CN107075279A - The contamination control coating composition of polymer comprising the polymer containing monosilane ester group and containing quaternary ammonium/Phosphonium sulfonate groups - Google Patents
The contamination control coating composition of polymer comprising the polymer containing monosilane ester group and containing quaternary ammonium/Phosphonium sulfonate groups Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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- C09D5/165—Macromolecular compounds containing hydrolysable groups
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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Abstract
The present invention relates to contamination control coating composition, it includes the composition with biocidal properties；And (a1) includes quaternary ammonium group and/or the season for the main chain for being bound to polymerThe polymer of group, the quaternary ammonium group and/or season
Description
The people in water is immersed in the invention additionally relates to contamination control coating composition (particularly for ocean application), protection
The method of structure is made, and is coated with the base material or structure of the contamination control coating composition.
Background and summary
It is immersed in man-made structures (such as shell, buoy, drilling platform, Petroleum Production rig and pipeline) Yi Shoushui in water
The pollution of raw biological (such as green alga and brown alga, barnacle, mussel and such).The structure is generally made, but also may be used by metal
Include other structural materials (such as concrete).This pollution has infringement to shell, because during which increasing and being moved by water
Frictional resistance, as a result makes speed reduce and fuel cost increase.It is to static structure (such as drilling platform and Petroleum Production rig
Supporting leg) have infringement, firstly because thick pollution layer can cause unpredictable and tool in the structure shown here to the resistance of wave and current
The stress being potentially dangerous, and secondly because pollution makes it difficult to the defect (such as stress fracture and corrosion) of inspection structure.Its
There is infringement to pipeline (such as cooling water inlet and outlet), because pollution reduces effective area of section, and flow velocity drops in result
It is low.
It is known to use contamination control paint as the table coating on (such as) shell, to suppress marine organisms (such as barnacle
And algae) settlement and growth, this is generally realized by the release of the biocides of marine organisms.
Generally, base-material of the contamination control paint comprising relative inertness and the biocidal pigment from paint leaching.Use
Base-material in particular vinylite and rosin.Vinylite is that seawater is insoluble, and the paint based on the resin is used
High pigment levelses between pigment particles to contact to ensure leaching.Rosin is hard brittle resin, and it is slightly dissolved in seawater.
Contamination control paint based on rosin has been referred to as dissolvable matrix or has corroded paint.Base of the biocidal pigment from rosin base-material used
Matter is gradually leached, and leaves the bone matrix of rosin, and the biocidal pigment is washed off deep from paint films to allow from hull surface
Locate leaching biocidal pigment.
Successful contamination control paint many in recent years are " from polishing polymer " paint, biocidal based on polymerization base-material
Three organotin parts polymerize base-material chemical bond with this and the biocidal moieties are gradually hydrolyzed from it by seawater.In the binder systems
In, the side base of straight chain polymer unit is divided by the reaction with seawater in the first step, as a result makes remaining polymer
Framework becomes with water dissolvable or water-dispersible.In the second step, water dissolvable ship oiled at the surface of enamelled coating
Or water-dispersible framework is washed off or corroded.The paint system in GB-A-1457590 such as (e.g.) being illustrated.Due to three organic
The use of tin is limited and will forbidden in the whole world by legislation, therefore needs the replacement that can be used in contamination control composition dirty in the industry
Dye control material.
Comprising the quaternary ammonium through acid blocked/The polymer of group is the example for including the base material polymer for blockading functional group,
As a result the blocking group of the polymer can make remaining polymer frame become solvable through seawater Substance P hydrolysis, dissociation or exchange
In or be dispersed among in seawater, the blocking group of the polymer has hypotoxicity, preferably non-biocidal.WO2004/
018533 illustrates that (that is, quaternary ammonium group is through monoesters carbonate anion comprising the quaternary ammonium group containing the conjugate base end-blocking through carboxylic acid
End-blocking) polymer contamination control coating composition.
Also the known polymer containing monosilane ester group can be used for from polishing contamination control paint system and be set forth in
In A1, the US 4,593,055 of WO 00/77102, US 5,436,284 and WO2005005516.
This document all do not teach comprising the polymer containing monosilane ester group and comprising sulfonic acid block quaternary ammonium/Polymerization
The preparation of the contamination control coating composition of the polymer of thing.
The present invention coating composition need sulfonic acid block quaternary ammonium/Polymer and the polymerization for including monosilane ester group
Thing.In surprise, it has been observed by the present inventors that the coating of the admixture comprising these polymer has better than poly- comprising these types
The contamination control performance of the coating of only one in compound.
In addition, the inventors have found that the contamination control coating of the present invention keeps stable, and with high integrality, i.e., specifically and
Speech when applying to alternately those wet and dry part (such as at the waterlines) of coating in a reservoir, its show almost without being broken and
Good adherence.In addition, the coating composition of the present invention shows fully short drying time.More specifically, coating of the invention
Composition has rapid draing after the application and the improvement of the stability during storing balance.
The present invention relates to contamination control coating composition, it includes composition and following polymer with biocidal properties：
(a1) quaternary ammonium group and/or season comprising the main chain for being bound to polymerThe polymer of group, the quaternary ammonium group
Group and/or seasonGroup is neutralized by the conjugate base of the sulfonic acid with aliphatic hydrocarbyl, aromatic hydrocarbyl or alkaryl hydrocarbon group, and
(a2) polymer of monosilane ester group is included.
The contamination control coating composition of the present invention formulated can cause it with the VOC less than 400g/l and at 25 DEG C
Less than the shear viscosity of 20 pools (poise).
The VOC content of composition can according to EPA reference methods 24 combine ASTM standard D3960-02 come measure or according to
ASTM standard D 5201-01 are calculated.Two methods produce similar results.When value is directed to Inventive polymers solution or coating group
When the viscosity of compound is provided, the shear viscosity that cone and plate viscometer is measured is used with reference to according to ASTM standard D 4287-00.
Generally, the conjugate base of sulfonic acid has aliphatic hydrocarbyl, aromatic hydrocarbyl or the alkaryl for including 6 or more carbon atoms
Alkyl.
Polymer (a2) comprising monosilane ester group can have the weight average molecular weight less than 70,000.Include monosilane ester
The polymer (a2) of group can have the weight average molecular weight more than 10,000 and less than 70,000.
The weight average molecular weight of polymer (a1) and polymer (a2) is measured and is used as by GPC (gel permeation chromatography) absolutely
Molecular weight is calculated.It can be obtained from GPC by three re-detection methods using the combination of light scattering, viscosimeter and concentration detector
Hexafluoroisopropanol (HFiP) can be used advantageously to implement polymer (a1) as solvent for absolute molecular weight and absolute weight average molecular
GPC.
Polydispersity (D) is also referred to as molecular weight distribution sometimes, and it is defined as the weight average molecular weight (Mw) of polymer to quantity
The ratio (D=Mw/Mn) of mean molecule quantity (Mn).Also polydispersity can be determined by GPC.
Polymer (a1) in contamination control coating composition:The weight ratio of polymer (a2) can be 1:20 to 20:1st, it is excellent
Select 1:4 to 4:1st, preferably 3:1 to 1:3 and most preferably 65:35 to 35:In the range of 65.
Polymer (a1) and/or polymer (a2) can be (methyl) acrylic acid series polymeric compounds.(methyl) acrylic polymeric
Thing mean can by acrylic acid, methacrylic acid or its salt, ester, acid amides or carbonitrile derivatives optionally with other one or more ethene
The polymer that the polymerization of base polymerisable monomer is obtained.(methyl) acrylic acid series polymeric compounds most typically be can be by acrylate monomer
(acrylic acid ester monomer) (" acrylate monomer (acrylate monomer) ") and/or methacrylic acid
Ester monomer (methacrylic acid ester monomer) (" methacrylate monomers (methacrylate
Monomer) ") and choose any one kind of them or various other vinyl polymerizable monomers polymerization obtain polymer.
Therefore, polymer (a1) can be comprising thereon with quaternary ammonium group and/or season(methyl) third of the side chain of group
Olefin(e) acid based polymer, the quaternary ammonium group and/or seasonGroup is by with aliphatic hydrocarbyl, aromatic hydrocarbyl or alkaryl hydrocarbon group
The conjugate base of sulfonic acid is neutralized.
Therefore, polymer (a2) can be (methyl) acrylic polymeric for including the side chain thereon with monosilane ester group
Thing.
Polymer (a1) can optionally include the monomers of one or more olefinic double bonds by formula (I) monomer with one or more
The polymerization of (" vinyl polymerizable monomers ") is obtained：
Wherein Y is O or NH,
Z+For N+Or P+,
R6For hydrogen atom or C1-C4Alkyl, preferably hydrogen or C1-C2Alkyl,
R7For C2Or C3-C12Divalent hydrocarbyl mission, preferably C2Or C3-C8Divalent hydrocarbyl mission, more preferably C2Or C3-C4Bivalent hydrocarbon radical
Group,
R8And R9Independently represent C1-C6Alkyl, preferably methyl, or the phenyl being optionally substituted,
R10For C1-C5Alkyl,
X- is the conjugate base of the sulfonic acid comprising aliphatic hydrocarbyl, aromatic hydrocarbyl or alkaryl hydrocarbon group.
The relative ion (i.e. X-) of polymer (a1) can be the conjugate base of the sulfonic acid comprising 6 to 50 carbon atoms.
Polymer comprising monosilane ester group (a2) preferably comprises at least a formula with least one end group
(II) side chain：
Wherein A is divalence-C (O)-or-S (O)2O- groups, n is 0 or 1 to 50 integer, and R1、R2、R3、R4And R5Each other
Independently selected from：The C being optionally substituted1-20Alkyl, the C being optionally substituted1-20Alkoxy, the C being optionally substituted1-20Aryl and
The C being optionally substituted1-20Aryloxy group.
Polymer (a2) can be (methyl) acrylic acid series polymeric compounds for including formula (II) side chain.
Generally, n=0 and R3、R4And R5Identical or different and expression methyl, isopropyl, normal-butyl, isobutyl group or phenyl.
Contamination control coating composition can further include rosin material and/or non-hydrolyzable water-insoluble film forming polymer
(a3).Non-hydrolyzable water-insoluble film forming polymer (a3) can be acrylate polymer or vinylic-ether polymer.
Contamination control coating composition can have at least 55 weight % solids content.
The invention additionally relates to protect the man-made structures being immersed in water to exempt from contaminated method, it is achieved by the following way：
Contamination control coating composition as herein defined is applied to man-made structures, permissible contamination control coating composition formation is applied
Layer, and then coated man-made structures are immersed in water.The example of man-made structures is shell, buoy, drilling platform, oil
Produce rig and pipeline.
The invention additionally relates to be coated with the base material or structure of contamination control coating composition as set forth herein.
Describe in detail
The quaternary ammonium of sulfonic acid end-blocking/Polymer (a1)
Contamination control coating composition includes quaternary ammonium group and/or the season of the main chain containing polymer is bound toGroup
Polymer, the quaternary ammonium group and/or seasonGroup is total to by the sulfonic acid with aliphatic hydrocarbyl, aromatic hydrocarbyl or alkaryl hydrocarbon group
Yoke alkali is neutralized.The quaternary ammonium that this polymer quarter, referred to as sulfonic acid was blocked/Polymer.
The quaternary ammonium of sulfonic acid end-blocking/Polymer (a1) preferably has greater than 10,000 weight average molecular weight.For example, polymer
(a1) weight average molecular weight can be more than 10,000 and less than 90,000.
Ammonium group/Group is usually located on the side chain for the main chain for hanging on polymer.
Generally, the conjugate base of sulfonic acid is comprising aliphatic hydrocarbyl, aromatic hydrocarbyl or alkaryl hydrocarbon group (preferred aliphatic series) and includes 6
Or more carbon atom.
The ammonium of sulfonic acid end-blocking/Polymer can be obtained by the following processing procedure comprised the steps of：
1. amine function or phosphine functional monomer using the quaternized formula of dialkyl carbonate (III)：
Each of which alkyl independently is C1-C5Alkyl
Wherein
Y is O or NH, Z are N or P, R6For hydrogen atom or C1-C4Alkyl, preferably hydrogen or C1-C2Alkyl,
R7For C2Or C3-C12Divalent hydrocarbyl mission, preferably C2Or C3-C8Divalent hydrocarbyl mission, more preferably C2Or C3-C4Bivalent hydrocarbon radical
Group,
R8And R9Independently represent C1-C6Alkyl, preferably methyl, or the phenyl being optionally substituted,
2. replaced with the sulfonate relative ion derived from the sulfonic acid with aliphatic hydrocarbyl, aromatic hydrocarbyl or alkaryl hydrocarbon group
The quaternized ammonium of gained/The relative ion of monomer.It is preferred that, sulfonic acid includes the aliphatic hydrocarbon for preferably comprising 6 or more carbon atoms
Group.The quaternary ammonium that this generation is blocked through relative ion/Monomer, wherein relative ion by sulfonic acid conjugate base (anion residue)
Constitute, the conjugate base of sulfonic acid includes the aliphatic hydrocarbon group for preferably comprising 6 or more carbon atoms preferably wherein.
3. make sulfonic acid block quaternary ammonium/At least one polymerization in monomer.
Can be by making formula (III) monomer and dialkyl carbonate react amine function or the phosphine functional monomer of implementation formula (III)
Quaternized [step 1], each of which alkyl independently is C1-C5Alkyl.Dialkyl carbonate can be (for example) carbonic acid diformazan
Ester, ethyl methyl carbonate, diethyl carbonate or dipropyl carbonate.Most preferably dimethyl carbonate.
Using the amine/phosphine functional monomer of the quaternized formula of dialkyl carbonate (III) produce the quaternary ammonium of formula (IV)/Function list
Body：
Wherein
Y is O or NH,
Z+For N+Or P+,
R6For hydrogen atom or C1-C4Alkyl, preferably hydrogen or C1-C2Alkyl,
R7For C2Or C3-C12Divalent hydrocarbyl mission, preferably C2Or C3-C8Divalent hydrocarbyl mission, more preferably C2Or C3-C4Bivalent hydrocarbon radical
Group,
R8And R9Independently represent C1-C6Alkyl, preferably methyl, or the phenyl being optionally substituted,
R10For C1-C5Alkyl, preferably R5For methyl,
And W- is [O-C (O)-R11]-Anion, wherein R11For monovalent alkyl (such as C1-C3Alkyl).(i.e. W- is monoesters
Carbanion)
Reaction condition can be as being directed to tertiary amine R in EP-A-291074xRyRzN (wherein Rx、RyAnd RzRepresent hydrocarbon residue) quaternary ammonium
Change is illustrated.For example, the amine functional monomer of formula (III) and dialkyl carbonate can be used with 0.2 to 5 mol ratio.Generally, should
Reaction can in the presence or absence of a solvent be carried out under 20 DEG C to 200 DEG C of reaction temperature.
It is preferred that, in about 90psi to 100psi (6.1 in the presence of alcohol, preferably methanol at a temperature of 115 DEG C to 135 DEG C
105Pa to 6.8105Pa the reaction is implemented under increased pressure).
The usable sulfonic acid implementation ammonium with aliphatic hydrocarbon group, aromatic hydrocarbon radical or alkaryl hydrocarbon group group/The carbon of monomer
The replacement [step 2] of acid esters relative ion.
It is preferred that, the hydrocarbyl group of sulfonic acid includes 6 or more carbon atoms, more preferably 8 or more carbon atoms.Sulfonic acid
Hydrocarbyl group preferably comprises at most 50 carbon atoms, even more preferably at most 30 carbon atoms, and most preferably up to 20 carbon atoms.
The quaternary ammonium of sulfonic acid end-blocking/The polymerization [step 3] of functional monomer can by make sulfonic acid block quaternary ammonium/Function
(vinyl polymerizable monomers are the list with one or more olefinic double bonds to monomer with one or more vinyl polymerizable monomers
Body) react to implement.
Therefore, can by make sulfonic acid block quaternary ammonium/Functional monomer's (it can have the structure of formula (I)) and one kind or many
Plant vinyl polymerizable monomers polymerization and obtain polymer (a1).
The example of vinyl polymerizable monomers includes (methyl) acrylate, such as methyl methacrylate, metering system
Acetoacetic ester, butyl methacrylate, methacrylic acid 2- ethylhexyls, methacrylic acid 2- hydroxyethyls ester and metering system
Sour methoxy ethyl ester；Maleate, such as dimethyl maleate and diethyl maleate；Fumarate, such as fumaric acid two
Methyl esters and diethyl fumarate；Styrene, vinyltoluene, Alpha-Methyl-styrene, vinyl chloride, vinyl acetate, butadiene,
The different camphyl ester of acrylamide, acrylonitrile, methacrylic acid, acrylic acid, methacrylic acid, maleic acid and its mixture.
It is preferred that, one or more vinyl polymerizable monomers are comprising (methyl) acrylic acid with having 4 or more carbon former
The ester of the alcohol of son.The example of (methyl) acrylic acid and the suitable ester of the alcohol with 4 or more carbon atoms includes (methyl) third
Olefin(e) acid n-butyl, (methyl) i-butyl base ester, (methyl) acrylate tert-buthyl, (methyl) acrylic acid n-pentyl ester,
(methyl) acrylic acid isoamyl base ester, (methyl) acrylic acid neopentyl ester, (methyl) acrylic acid n-hexyl ester, (methyl) acrylic acid are different
Hexyl ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) propylene
Sour ethylhexyl, (methyl) acrylic acid octyl group ester, (methyl) acrylic acid camphyl ester and the different camphyl ester of (methyl) acrylic acid.Cause
This, can by make sulfonic acid block quaternary ammonium/Functional monomer and at least (methyl) butyl acrylate cores or (methyl) acrylic acid are different
Camphyl polyisocyanate polyaddition obtains polymer (a1).The monomer is relative hydrophobicity.Can be by using hydrophobicity and hydrophily (methyl)
The polishing speed of the mixture adjusting coating of acrylate monomer.The example of optional hydrophily co-monomer is (methyl) acrylic acid first
Epoxide ethyl ester or more senior polyethylene oxygen derivative (such as (methyl) ethioxy ethyl ester), (methyl) acrylic acid third
Epoxide ethyl ester, (methyl) butoxyethyl acrylate, polyoxy ethylene glycol monoalkyl ether (methyl) acrylate (for example gather
Epoxide ethylene glycol (n=8) monomethyl ether methacrylate) or NVP.Therefore, can be by blocking sulfonic acid
Quaternary ammonium/Functional monomer polymerize acquisition polymer with the mixture of hydrophobicity and hydrophily (methyl) acrylate monomer
(a1)。
Another selection is, can by containing the quaternary ammonium group blocked through monoesters carbonate anion/The polymer of group
The ammonium blocked with the reaction acquisition sulfonic acid of the sulfonic acid with aliphatic hydrocarbyl, aromatic hydrocarbyl or alkaryl hydrocarbon group/Polymer.Reason
Think ground, hydrocarbyl group includes 6 or more carbon atoms.
The speed for dissolving or corroding in seawater, and substantially nothing can be painted by the structure regulation present invention of blocking group
The problem of related to the toxicity of discharged group.It is preferred that, blocking group has comprising one or more includes 6 to 50 carbon originals
The sour anion residue of son, the aliphatic hydrocarbon group of more preferably 6 to 20 carbon atoms.
Implement addition copolymerization using any one in above-mentioned vinyl polymerizable monomers.Can be by making alkyl, alcoxyl
The ester or acid amides of base alkyl, carbocyclic ring or heterocyclic alcohol or amine and unsaturated carboxylic acid reaction prepare vinyl polymerizable monomers, such as third
E pioic acid methyl ester or methyl methacrylate, butyl acrylate or butyl methacrylate, i-butyl base ester or metering system
Sour isobutyl and the different camphyl ester of acrylic acid or the different camphyl ester of methacrylic acid.
Polymer (a2) comprising monosilane ester group
Polymer (a2) comprising monosilane ester group preferably has greater than 10,000 weight average molecular weight.It is preferred that, polymerization
The weight average molecular weight of thing (a2) is more than 20,000 and less than 70,000.
Polymer (a2) preferably has greater than 1.1 polydispersity；Polydispersity is preferably smaller than 3.0, even more preferably small
In 2.8.
It is preferred that, polymerization when formed the polymer (a2) monomer be more than 10 weight %, even more preferably greater than 30 weights
Measure % and the highly preferred 40 weight % that are more than provide the side chain with monosilane ester functional group.It is preferred that, polymerization when formed this gather
The 70 weight %, even more preferably less than 60 weight % that are less than of the monomer of compound (a2) provide the side with monosilane ester functional group
Chain.
Polymer (a2) comprising monosilane ester group preferably comprises at least a formula with least one end group
(II) side chain：
Wherein A is divalence-C (O)-or-S (O)2O- groups, n is 0 or 1 to 50 integer, and R1、R2、R3、R4And R5Each other
Independently selected from：The C being optionally substituted1-20Alkyl, the C being optionally substituted1-20Alkoxy, the C being optionally substituted1-20Aryl and
The C being optionally substituted1-20Aryloxy group.
It is preferred that, n=0 and R3、R4And R5Identical or different and expression methyl, isopropyl, normal-butyl, isobutyl group or phenyl.
In the context of the present invention, term C1-20Alkyl represents the straight chain with 1 to 20 carbon atom, tool side chain and ring-type
Hydrocarbyl group, such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, hexyl, hexamethylene
Base, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, octadecyl and eicosane
Base.The C that term is substituted1-20Alkoxy means C1-20Alkyl oxy, such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, just
Butoxy, isobutoxy, secondary amine epoxide, tertiary amine epoxide, amoxy, hexyloxy, cyclohexyloxy, epoxide in heptan, octyloxy, nonyl oxygen
Base, decyloxy, hendecane epoxide, dodecyloxy, tetradecyloxyaniline, hexadecane epoxide, octadecane epoxide and eicosane epoxide.
Term aryl is understood to mean that aromatic carbocyclic or loop system, such as phenyl, naphthyl, xenyl and xylyl.Term is " optionally
Be substituted " be used for indicate the group can be substituted base substitution it is one or many, preferably 1 to 5 time.The substituent can be for (for example)
Hydroxyl, alkyl, hydroxy alkyl, alkyl carbonyl oxy, carboxyl, alkoxy carbonyl, alkoxy, alkenyloxy group, side epoxide, alkyl-carbonyl,
Aryl, amino, alkyl amino, carbamoyl, alkyl amino-carbonyl, aminoalkylamino-carbonyl, aminoalkylamino-carbonyl,
Alkyl-carbonyl amine, cyano group, guanidine radicals, urea groups, alkanoyloxy, sulfonyl, alkylsulfonyloxy, nitro, sulfenyl, alkyl sulfenyl and halogen
Element.
Can be by making (i) one or more vinyl polymerizable monomers and (ii) one or more include monosilane ester group
And the monomer polymerization of one or more olefinic double bonds obtains the polymer (a2) for including monosilane ester group.
Example available for the vinyl polymerizable monomers for preparing polymer (a2) prepares polymer (a1) with can be used for
Vinyl polymerizable monomers are substantially the same and including (such as) (methyl) acrylic acid series polymeric compounds, such as methacrylic acid, third
Olefin(e) acid；(methyl) acrylate, such as methyl methacrylate, EMA, butyl methacrylate, metering system
Sour 2- ethylhexyls, (methyl) n-butylacrylate, (methyl) i-butyl base ester, (methyl) acrylic acid tert-butyl group
Ester, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid isoamyl base ester, (methyl) acrylic acid neopentyl ester, (methyl) propylene
Sour n-hexyl ester, (methyl) acrylic acid dissident base ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (first
Base) phenyl acrylate, (methyl) ethylhexylacrylate, (methyl) acrylic acid octyl group ester, (methyl) acrylic acid camphyl ester
And the different camphyl ester of (methyl) acrylic acid, (methyl) methoxyethyl ethyl ester；Or more senior polyethylene oxygen derivative, for example
(methyl) ethioxy ethyl ester, (methyl) acrylic acid Among ester, (methyl) butoxyethyl acrylate, first
Base acrylic acid 2- hydroxyethyls ester, polyoxy ethylene glycol monoalkyl ether (methyl) acrylate (such as polyoxy ethyl glycol (n=
8) monomethyl ether methacrylate)；Maleic acid and maleate, such as maleic acid dimethyl esters and maleic acid diethyl ester；
Fumaric acid and fumarate, such as dimethyl fumarate and diethyl fumarate；Styrene；Vinyltoluene；Alpha-Methyl-benzene second
Alkene；Vinyl chloride；Vinyl-acetic ester；Butadiene；Acrylamide；Acrylonitrile；NVP；And its mixture.
The example of suitable monomer comprising monosilane ester group and one or more olefinic double bonds includes the monomer of formula (V)：
Wherein R3、R4And R5It is each independently selected from：The C being optionally substituted1-20Alkyl, the C being optionally substituted1-20Alcoxyl
Base, the C being optionally substituted1-20Aryl and the C being optionally substituted1-20Aryloxy group, and X is (methyl) acryloxy, Malaysia acyl-oxygen
Base, fumaroyl epoxide or clothing health acyloxy.
It is preferred that, n=0 and R3、R4And R5Identical or different and expression methyl, isopropyl, normal-butyl, isobutyl group or phenyl.
The preparation of formula (V) monomer can be (for example) according to the method that is set forth in EP 0 297 505 or according to being set forth in EP 1
273 589 and wherein cited bibliography in method implement.Therefore, the polymer comprising monosilane ester group can be
(methyl) acrylic acid series polymeric compounds comprising monosilane ester group.
Monomer comprising monosilane ester group and one or more olefinic double bonds be the following in one：(first
Base) acrylic acid trimethyl silyl ester, (methyl) acrylic acid silicohetane alkyl ester, (methyl) acrylic acid three-n-propyl first silicon
Alkyl ester, (methyl) acrylic acid triisopropyl monosilane ester, (methyl) acrylic acid three-normal-butyl monosilane ester, (methyl) acrylic acid
Triisobutyl monosilane ester, (methyl) acrylic acid three-tert-butyl group monosilane ester, (methyl) acrylic acid three-n-pentyl monosilane ester,
(methyl) acrylic acid three-n-hexyl monosilane ester, (methyl) acrylic acid three-n-octyl monosilane ester, (methyl) acrylic acid three-just
Dodecyl monosilane ester, (methyl) acrylic acid triphenylsilyl ester, (methyl) acrylic acid three-p-methylphenyl monosilane
Ester, (methyl) acrylic acid tribenzyl monosilane ester, (methyl) acrylic acid dimethylphenylsilane ester, (methyl) acrylic acid diformazan
Cyclohexyl acetate, (methyl) acrylic acid ethyl dimethyl silane ester, (methyl) acrylic acid normal-butyl dimethyl silane ester,
(methyl) acrylic acid t-butyl-dimethylsilyl ester, (methyl) acrylic acid diisopropyl-normal-butyl monosilane ester, (methyl) third
Olefin(e) acid n-octyl di-n-butyl monosilane ester, (methyl) acrylic acid diisopropyl stearyl monosilane ester, (methyl) acrylic acid two
Cyclohexyl phenyl monosilane ester, (methyl) acrylic acid t-butyidiphenylsilyl ester and (methyl) lauryl base diphenyl
Monosilane ester.It is preferred that, from (methyl) acrylic acid triisopropyl monosilane ester, (methyl) acrylic acid tributylsilyl ester or (first
Base) at least one preparation in acrylic acid triisobutyl monosilane ester monomer includes the polymer (a2) of monosilane ester group.
In general, preparing molecule measurer of the reaction temperature to polymer of the polymer (a2) comprising monosilane ester group
Have an impact.Other or another selection is also can be by the amount of initiator used and/or by adding chain-transferring agent (such as mercaptan)
Adjust molecular weight.The patterns affect polydispersity of initiator.For example, can be by selecting azo initiator (such as azo pair-isobutyl
Nitrile or azo pair-methylbutyronitrile) reduction polydispersity.Another selection is or in addition, can adjust the solvent reacted wherein
To adjust the molecular weight and its polydispersity of polymer.
Can be by adjusting the molecular weight of polymer and/or by adjusting its polydispersity and/or by adjusting solids content
To adjust the viscosity of the polymer solution comprising monosilane ester group and/or coating composition.
Optional component：
Contamination control coating composition, which can be included in seawater, has seawater reactive and/or slightly soluble or water sensitive
Other resins of property.
These other resins can form the at most 50 weight % of the gross weight of coating composition.
Other seawater reactive polymers
Coating composition can optionally include other seawater reactive polymers.One example is sour function film forming polymer,
Its acid groups is by that can hydrolyze or dissociate so that so that the group that polymer is dissolved in seawater is blockaded, blocking group is selected from key
Tie to the divalent metal atom of the divalent metal atom of monovalent organic residue, bond to OH residues, and form having for polymer
The monoamine group of machine solvent soluble amine salt, as illustrated in WO 00/43460.For example, this seawater of acid groups through blockading
Reactive acid function film forming polymer can be the polymerization of at least one side chain with the end group with least one following formula
Thing：
Wherein X is represented
M is the metal selected from zinc, copper and tellurium；X is 1 to 2 integer；R represents to be selected from
OR1 ,-SR1 orOrganic residue；
And R1 is monovalent organic residue, as illustrated in EP-A-204456.
This hydrolyzable preferred acrylic acid series polymeric compounds of polymer, wherein X is represented
M is copper, and R is representedWith-COOH group and non-X- [O-M-R]nParent third
Olefin(e) acid based polymer preferably has 25-350mg KOH/g acid number.Most preferably, hydrolyzable polymer has 0.3 weight % extremely
20 weight % copper content and R1 is the residue of higher boiling organo units acid.The hydrolyzable polymer can be by being disclosed in EP 0
It is prepared by processing procedure in 204 456 and EP 0 342 276.The film forming polymer of cupric is preferably to include acrylic acid or methyl-prop
The polymer of olefin(e) acid ester, its alcohol residue includes bulky alkyl and rolled into a ball or soft chain segment, for example the tool branch with 4 or more carbon atoms
Alkane base ester or cycloalkyl ester, the optional poly- alkane glycol list third with end alkyl ether group with 6 or more atoms
Olefin(e) acid ester or monomethacrylates, or acrylic acid 2- hydroxyethyls ester or methacrylic acid 2- hydroxyethyls ester and caprolactone
Adduct, as illustrated in EP 0,779 304.
Another selection is that seawater reactivity sour function film forming polymer of this acid groups through blockading can be poly- for carboxylic-acid functional
Compound.For example, it can be acrylic or methacrylic acid and one or more alkyl acrylates or alkyl methacrylate
Polymer, its at least some acid groups converted group for formula-COO-M-OH, wherein M be divalent metal (for example copper, zinc,
Calcium, magnesium or iron), as illustrated in GB 2,311,070.
Another example of seawater reactivity sour function film forming polymer of this acid groups through blockading is the polymerization of the salt of amine
Thing.It is preferred that, it is the salt and such as EP 0 529 693 of the amine containing at least one aliphatic hydrocarbon group with 8 to 25 carbon atoms
Middle illustrated sour function film forming polymer, the acid functional polymers are preferably alkene system unsaturated carboxylic acid, sulfonic acid, bisulphate
The addition polymer of the unsaturated co-monomer of ester, phosphonic acids or phosphate ester acid and at least one alkene system, unsaturated carboxylic acid is (for example)
Acrylic or methacrylic acid, unsaturated sulfonic acid is (for example) 2- acrylamidos -2- methyl propane sulfonic acids (AMPS), and this into
Membrane polymer is preferably the amine sulfonate polymers of the unit containing organic cyclic ester as illustrated in WO 99/37723.
There are other resins of slightly soluble or water sensitivity in the seawater
Coating composition can be optionally included in other resins in seawater with slightly soluble or water sensitivity.It can be mentioned that
Following compound is used as the suitable polymer or the example of resin in the seawater with slightly soluble or water sensitivity：Vinyl
Ether polymer, such as poly- (vinyl alkyl ethers), such as polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl propyl group
Ether and polyvinyl isobutyl ether, or vinyl alkyl ethers and vinyl acetate or the polymer of vinyl chloride；Alkyd resin, through changing
Matter alkyd resin；Polyurethanes；Saturated polyester resin；Poly-N-vinyl pyrrolidones；Epoxy polymer；Epoxy-ester；Ring
Oxygen carbamate；Linseed oil, castor oil, soybean oil and the oily derivative；Acrylate polymer, such as it is a kind of or many
Kind containing 1 to 6 carbon atom and can contain such as acrylonitrile or the alkyl acrylate of styrene co-monomer preferably in alkyl
Or the homopolymer or polymer of alkyl methacrylate；Vinyl acetate polymer, such as polyvinyl acetate or acetic acid second
Alkene ester vinyl chloride-base polymer；Polyamine, the specifically polyamide with plasticization effect, such as the polyamide of fatty acid dimer or
The polyamide sold with trade (brand) name " Santiciser ", and rosin material.
This rosin material is preferably rosin, and specifically wood rosin or another selection is tower sieve rosin (tall rosin)
Or resin.The primary chemical component of rosin is resin acid.Rosin can be commercially available any rank, preferably as WW (water-white)
Rosin seller.Another selection is that rosin material can be rosin derivative, such as maleylation or fumarylated rosin, hydrogenation pine
Fragrant, formylated rosin or newtrex, or rosin metal salt, such as rosin acid calcium, rosin acid magnesium, copper abietinate or rosin acid
Zinc.
Optional additive：
May be added to that additive in contamination control coating composition include reinforcing agent, stabilizer, thixotrope or thickener,
Plasticiser, liquid carrier and non-biocidal pigment.
The example that may be added to that suitable reinforcing agent in contamination control coating composition is fiber, such as carbide fibre,
Containing silica fibre, metallic fiber, carbon fiber, sulphide fibres, phosphate fiber, Fypro, aromatic polyhydrazide fibre, aromatics
Polyester fiber, cellulose fibre, IR fiber, acrylic fiber, polyvinyl chloride fibre and polyethylene fibre.It is preferred that, fiber tool
There are 25 microns to 2,000 micron of average length and 1 micron to 50 microns of average thickness, and average length and average thickness
Ratio is at least 5.
The example of suitable stabilizer is moisture scavenger, zeolite, aliphatic series or aromatic amine (such as dehydroabietylamine), orthosilicic acid
Tetra-ethyl ester and triethyl orthoformate.
The example of suitable thixotrope or thickener is silica, hundred logical (bentone) and polyamide waxes.
The example of suitable non-polymeric plasticiser is phthalic acid ester (such as dibutyl phthalate, phthalic acid
Butyl ester benzyl ester or dioctyl phthalate), the ester of phosphate three (such as tricresyl phosphate or tricresyl phosphate (isopropyl) benzene
Base ester) or chlorinated paraffin and sulfonamide (toluenesulfonamide of such as N substitutions).
This plasticiser (for example) can be present in painting by the at most weight % of 50 weight %, most preferably at least 5% and at most 25
In feed composition.
The example of appropriate liquid supporting agent is organic solvent, organic non-solvents and water.The Sutable examples of organic solvent are aromatics
Hydrocarbon (such as dimethylbenzene, toluene or trimethylbenzene), alcohol (such as n-butanol), ether alcohol (such as butyl cellosolve or methoxy propyl
Alcohol), ester (such as butyl acetate or isoamyl acetate), ether-ether (such as acetic acid ethoxyethyl group ester or acetic acid methoxy-propyl
Ester), ketone (such as methyl iso-butyl ketone (MIBK) or methyl isoamyl ketone), in aliphatic hydrocarbon (such as petroleum solvent) or the solvent both or
The mixture of more persons.Coating can be scattered in the organic non-solvents for the film forming component in coating composition.Another choosing
It is selected as, coating may be based on water；For example, it can be based on aqueous liquid dispersion.
The example that may be added to that the non-biocidal pigment in coating composition is the non-biocide of slightly seawater-soluble
Insoluble non-biocide (such as filler and coloring pigment (such as titanium dioxide of (such as zinc oxide and barium sulfate) and seawater
Titanium, iron oxide, phthalocyanine compound and AZOpigments)).The highly insoluble pigment preferably being less than with total pigment component of paint
60 weight %, more preferably less than 40% use.
Coating composition can have 30% to 60% pigment volume concentration (PVC).
Composition with biocidal properties
The biocide of aquatile is usually directed to the composition for killing marine organisms performance.Conventional paint can be used to mix
With technology by this biocide and mixed with polymers.When with the composition of marine organisms performance is killed for pigment, it can be paint
Pigment all or part of.
Biocide of the present invention can be the inorganic biocidal agent for marine organisms or limnobios, organic metal biocidal
Agent, metal-one of organic biocide or organic biocide or many persons.The example of inorganic biocidal agent include copper metal and
Mantoquita, such as cupric oxide, cuprous sulfocyanide, bronze, copper carbonate, copper chloride, corronil and silver salt (such as silver chlorate or nitric acid
Silver)；Organic metal and metal-organic biocide, including pyrithione (zinc salt of 2-pyridinethiol-1-oxide), pyridine
Thioketones copper, N- cyclohexyl-diazonium twoPairing copper, ethylidene-bis- (aminodithioformic acids) zinc (i.e. zineb (zineb)),
PZ (ziram (ziram)), and ethylidene-bis- (aminodithioformic acids) with zinc salt misfit
Manganese (i.e. Mancozeb (mancozeb))；And organic biocide, including formaldehyde, dodine mono-hydrochloric salts, Apl-Luster
(thiabendazole), N- trihalomethyls thiophthalimide, trihalomethyl thiosulfonamides, N- aryl Malaysia acyl
Imines (such as N- (2,4,6- trichlorophenyls) maleimide), 3- (3,4- dichlorophenyls) -1,1- dimethyl urea (diuron
(diuron)), 2,3,5,6- tetra- chloro- 4- (methyl sulphonyl) pyridine, 2- methylsulfany -4- butylamino -6- cyclopropylaminos -
S- triazines, 3- benzos [b] thiophene-base -5,6- dihydro -1,4,2- oxa-thiazine 4- oxides, the chloro- 2- (n-octyl) -3 of 4,5- bis-
(2H)-isothiazolone, the different phthalonitrile of 2,4,5,6- tetrachloros, tolyfluanid (tolylfluanid), Euparen
(dichlofluanid), diiodomethyl-p-tolys, lfone sulfonyl sulfone, capsaicine, positive cyclopropyl-N '-(1,1- dimethyl ethyls)-
6- (methylsulfany) -1,3,5- triazine -2,4- diamines, the iodo- 2-propynyl butyl esters of carbamic acid 3-, dexmedetomidine
(medetomidine), 1,4- anthraquinone dithios -2,3- dimethoxy nitriles (Delan (dithianon)), borine (such as pyridine triphen
Base borine), at 5 and optionally in 1 halogen methyl -3- halogen -4- cyano pyrrole derivatives (such as 2- of the 2- being substituted tri-
The bromo- 5- trifluoromethyl pyrpoles (tralopyril) of (p- chlorphenyl) -3- cyano group -4-), and furanone (such as 3- butyl -5- (two
Bromine methylene) -2 (5H)-furanones), and its mixture, macrolide (such as AVM (avermectin), such as AVM hereinafter
Rhzomorph B1, ivermectin (ivermectin), doramectin (doramectin), Abamectin (abamectin), Ah Ma gram fourth
(amamectin) and selamectin (selamectin)), and quaternary ammonium salt (such as DDAC and alkyl-dimethyl
Base benzyl ammonium chloride).
In the context of the present invention, inorganic biocidal agent is chemical constitution killing comprising metallic atom and non-carbon atoms
Biological agent；Organic metal biocide is the biocide that chemical constitution includes metallic atom, carbon atom and metal-carbon bond；
Metal-organic biocide is chemical constitution comprising metallic atom, carbon atom and is free of the biocide that metal-carbon is bonded；And
Organic biocide is biocide of the chemical constitution comprising carbon atom and without metallic atom.
In addition, biocide optionally fully or partly encapsulated, absorption or support or can be combined.Some biocides
Disposal it is more difficult or dangerous and advantageously with it is encapsulated absorb or support or combining form use.In addition, biocide
It is encapsulated, absorbs or supports or combination can provides control from the biocide leaching rate of coating system to realize even more gradually
Release and permanent effect secondary mechanism.
The method for being encapsulated, adsorbing or supporting or combine of biocide is for the present invention and non-specifically is limited.It can prepare
Example for the mode of the encapsulated biocide of the present invention is included such as the single wall and double-walled ammonia that are illustrated in EP1791424
Base-formaldehyde or through hydrolyzed poly vinyl acetate-phenolic resin capsule or microcapsules.
Can prepare through absorb support or combine biocide mode example including the use of host-guest coordination compound (for example
Such as the clatraten illustrated in EP0709358), the phenolic resin as illustrated in EP0880892, the adsorbent based on carbon
(such as those of being set forth in EP1142477) or inorganic microporous supporting agent (are for example set forth in the amorphous dioxy in EP1115282
SiClx, amorphous alumina, false boehmite or zeolite).
The present invention is illustrated with reference to following examples.The embodiment is intended to the explaination present invention but is not regarded as limiting in any manner
The scope of the present invention processed.
Embodiment
The preparation of 1-polymer of embodiment (a1)
The quaternized monomer of sulfonic acid end-blocking is prepared in the following manner：
Dimethylaminopropyl Methacrylamide (192.1g), dimethyl carbonate (179.6g) and methanol (208g) are put
In stainless steel high-pressure reaction vessel.Sealing container is heated to 125 DEG C and kept for 4 hours.Filtering is through cooling down solution and adding
Plus be dried in a vacuum after methanol (150g).
The gained viscosity being substantially made up of corresponding alkyl trimethyl ammonium carbonate (244.7g) is diluted with dimethylbenzene (200g)
Amber color liquid is simultaneously placed in 2L round-bottomed flasks.Detergent alkylate was added into this through 30 minutes under agitation at room temperature
Solution of the sulfonic acid (244.7g) in dimethylbenzene (200g), and continue to be stirred overnight with provide the quaternized monomer of sulfonic acid end-blocking in
Solution in dimethylbenzene.
Through the addition into the stirring polymerization container containing dimethylbenzene (325.9g) with constant rate of speed in 5 hours at 85 DEG C
The solution of the monomer consisted of：Quaternized monomer (474.5g), the metering system of the sulfonic acid end-blocking prepared as explained above
The different camphyl ester (217.6g) of acid, butyl methacrylate (139.2g) and 2,2 '-azo two (2- methylbutyronitriles) (AMBN) rise
Solution of the beginning agent (4.7g) in dimethylbenzene (42.4g).Temperature is increased to 95 DEG C, and addition AMBN (2.35g) is in dimethylbenzene
Solution in (21.15g), and reaction vessel is maintained 2 hours at this temperature.Reaction vessel is set to be cooled to room temperature poly- to provide
Polymer solution 1.
The preparation of embodiment 2-polymer (a2) comprising monosilane ester group
Added at 85 DEG C through 3.5 hours with constant rate of speed into the stirring polymerization container containing dimethylbenzene (250.0g)
Methylate methyl acrylate (282.0g), methoxyethyl ethyl ester (30.6g) and acrylic acid triisopropyl monosilane ester
The solution of (375.3g) and AMBN (9.0g) in dimethylbenzene (81.3g).Temperature is increased into 95 DEG C, and addition AMBN (4.5g)
Solution in dimethylbenzene (40.6g), and reaction vessel is maintained 2 hours at this temperature.Reaction vessel is set to be cooled to room temperature
To provide polymer solution 2.
Embodiment 3-5-paint formulation agent
Mix following material to form containing for embodiment 3,4 and 5 with the parts by weight (pbw) using high speed disperser
The contamination control paint of copper.The paint formulation agent of embodiment 3 meets the present invention.The paint formulation agent of embodiment 4 and 5 is contrast
Example, because it only contains one in two kinds of polymer.
Anti-pollution (contamination control) is tested
Preparaton is applied to 60 × 60cm marine plywoods panel by roller to obtain about 150 microns of thickness of dry film,
Carry out anti-pollution (contamination control) performance of the paint formulation agent of comparing embodiment 3 and the comparison paint formulation agent of embodiment 4 and 5.
The plate has been pre-coated with Interprotect epoxy primers (International Paint Co., Ltds).Make each coating in ring
It is fully cured under the conditions of border, starts test afterwards.
By test panel while immersed in the waters at Hartlepool (UK) place, and it is also tight while immersed in known growth
Depth of the atural beat with 0.54m in maritime waters to 1.0m in the Changi of weight, Singapore.Periodically moved from water
Except the panel is to be taken a picture, and the pollution level before the panel is submerged again on evaluation coating.
In UK and Singapore waters, show from the coating of the formation of the embodiment of the present invention 3 and be less than from embodiment 4 and 5
The pollution of the comparison coating of formation.
The preparation of embodiment 6-polymer (a3) comprising the quaternary ammonium group neutralized by the conjugate base of carboxylic acid
The general procedure that is illustrated of preparation for following the quaternized monomer blocked in embodiment 1 for sulfonic acid prepares carboxylic acid
The quaternized monomer of end-blocking, simply replaces sulfonic acid, DBSA, to carry on the basis of equimolar with carboxylic acid, palmitic acid
For solution of the carboxylic acid-terminated quaternized monomer in dimethylbenzene.
Then follow seals carboxylic acid for the general procedure that is illustrated of preparation of polymer solution 1 (a1) in embodiment 1
The quaternized monomer polymerization at end, simply replaces the quaternary ammonium that sulfonic acid is blocked on the basis of equimolar with carboxylic acid-terminated quaternized monomer
Change monomer to provide polymer solution 3.
The preparation of embodiment 7-polymer (a4) comprising monosilane ester group
Through the addition into the stirring polymerization container containing dimethylbenzene (172.4g) with constant rate of speed in 4 hours at 80 DEG C
Methyl methacrylate (72.9), methoxyethyl ethyl ester (10.8g) and acrylic acid triisopropyl monosilane ester
The solution of (114.5g) and AMBN (2.1g) in dimethylbenzene (19.3g).AMBN (1.1g) is added in dimethylbenzene (40.6g)
Temperature is simultaneously increased to 95 DEG C by solution.Reaction vessel is maintained at this temperature 30 minutes.Make reaction vessel be cooled to room temperature with
Polymer solution 4 is provided.
Embodiment 8 and the agent of 9-paint formulation
Mix following material to form the pollution containing copper of embodiment 8 and 9 with the weight % using high speed disperser
Control paint.The paint formulation agent of embodiment 8 meets the present invention.The paint formulation agent of embodiment 9 is comparative example, wherein with bag
Polymer containing the quaternary ammonium group neutralized by the conjugate base of carboxylic acid replaces being used for including in the conjugate base of sulfonic acid in embodiment 8
The polymer of the quaternary ammonium group of sum.
Drying time tests
The oil that will be prepared using the square applicator with 300 Am nominal gap lengths in embodiment 8 and comparative example 9
Paint preparaton applies to 25mm is wide, 300mm length and the thick glass bars of 3mm.Follow and be set forth in ASTM D 5895-13:
Measuring Times of Drying or Curing During Film Formation of Organic Coatings
Program in Using Mechanical Recorders dries logger using BK at ambient room temperature and determines drying time.
| Embodiment 8 | Embodiment 9 | |
| Parch the time | 100 minutes | 160 minutes |
Show the coating being faster than from the formation of comparative example 9 from the coating of the formation of embodiment 8 and parch the time.
Storage stability is tested
The paint formulation agent that viscosity evaluation by periodically measuring paint is prepared in embodiment 8 and comparative example 9
Storage stability.Viscosity measurement is measured at 20 DEG C using Sheen Viscomaster CP1 cone and plate viscometers.In viscosity
Paint is stored during measurement in sealing canister at ambient room temperature.
| Embodiment 8 | Embodiment 9 | |
| Viscosity during manufacture | 5 pools | 5 pools |
| Viscosity after 14 days | 5 pools | Gel |
After 14 days, the paint formulation agent gelation that is prepared in comparative example 9 and and it can not reuse.By contrast, exist
The viscosity of the paint formulation agent prepared in embodiment 8 does not change, and paints still under usable situation.
Claims (13)
1. a kind of contamination control coating composition, it includes the composition with biocidal properties, and
(a1) quaternary ammonium group and/or season comprising the main chain for being bound to polymerThe polymer of group, the quaternary ammonium group and/
Or seasonGroup is neutralized by the conjugate base of the sulfonic acid with aliphatic hydrocarbyl, aromatic hydrocarbyl or alkaryl hydrocarbon group, and
(a2) polymer of monosilane ester group is included.
2. a kind of contamination control coating composition, the wherein conjugate base of sulfonic acid have the aliphatic series for including 6 or more carbon atoms
Alkyl, aromatic hydrocarbyl or alkaryl hydrocarbon group.
3. such as contamination control coating composition of claim 1 or 2, wherein the polymer (a2) comprising monosilane ester group has
Weight average molecular weight less than 70,000.
4. such as the contamination control coating composition of any one of preceding claims, it polymerize wherein in contamination control coating composition
Thing (a1):The weight ratio of polymer (a2) is 1:20 to 20:1, preferably 1:4 to 4:1.
5. such as the contamination control coating composition of any one of preceding claims, wherein polymer (a1) and/or polymer
(a2) it is (methyl) acrylic acid series polymeric compounds.
6. such as the contamination control coating composition of any one of preceding claims, wherein polymer (a1) can be single by formula (I)
Body optionally polymerize acquisition with one or more other monomers comprising one or more olefinic double bonds
Wherein Y is O or NH,
Z+For N+Or P+,
R6For hydrogen atom or C1-C4Alkyl, preferably hydrogen or C1-C2Alkyl,
R7For C2Or C3-C12Divalent hydrocarbyl mission, preferably C2Or C3-C8Divalent hydrocarbyl mission, more preferably C2Or C3-C4Divalent hydrocarbyl mission,
R8And R9Independently represent C1-C6Alkyl, preferably methyl, or the phenyl being optionally substituted,
R10For C1-C5Alkyl,
X-For the conjugate base of the sulfonic acid comprising aliphatic hydrocarbyl, aromatic hydrocarbyl or alkaryl hydrocarbon group.
7. relative ion (the X of the contamination control coating composition, wherein polymer (a1) such as any one of preceding claims-)
For the conjugate base of the sulfonic acid comprising 6 to 50 carbon atoms.
8. such as Contamination Coatings composition of any one of preceding claims, wherein the polymer (a2) comprising monosilane ester group
There is formula (II) side chain of at least one end group comprising at least one：
Wherein A is divalence-C (O)-or-S (O)2O- groups, n is 0 or 1 to 50 integer, and R1、R2、R3、R4And R5Independently of one another
Ground is selected from：The C being optionally substituted1-20Alkyl, the C being optionally substituted1-20Alkoxy, the C being optionally substituted1-20Aryl and optionally
The C being substituted1-20Aryloxy group.
9. contamination control coating composition as claimed in claim 8, wherein n=0, and R3、R4And R5Identical or different and expression first
Base, isopropyl, normal-butyl, isobutyl group or phenyl.
10. such as the contamination control coating composition of any one of preceding claims, it is further included
(a) rosin material and/or
(b) non-hydrolyzable water-insoluble film forming polymer (a3).
11. such as the contamination control coating composition of any one of preceding claims, gather wherein in contamination control coating composition
Compound (a1):The weight ratio of polymer (a2) is 1:4 to 4:In the range of 1.
12. a kind of protect the man-made structures being immersed in water to exempt from contaminated method, it is achieved by the following way：Will be such as claim
Any one of 1-10 contamination control coating composition applies to man-made structures, and permissible contamination control coating composition formation is applied
Layer, and then coated man-made structures are immersed in water.
13. a kind of base material or structure, it coats the contamination control coating composition just like any one of claim 1-11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14190685 | 2014-10-28 | ||
| EP14190685.9 | 2014-10-28 | ||
| PCT/EP2015/074691 WO2016066566A1 (en) | 2014-10-28 | 2015-10-26 | Fouling control coating compostion comprising a polymer containing silyl ester groups, and a polymer comprising quaternary ammonium/phosphonium sulphonate groups |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107075279A true CN107075279A (en) | 2017-08-18 |
| CN107075279B CN107075279B (en) | 2021-07-02 |
Family
ID=51795566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580057044.0A Active CN107075279B (en) | 2014-10-28 | 2015-10-26 | Pollution control coating composition comprising a polymer containing silyl ester groups and a polymer containing quaternary ammonium/phosphonium sulfonate groups |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US20170355861A1 (en) |
| EP (1) | EP3212719B1 (en) |
| JP (1) | JP6387187B2 (en) |
| KR (1) | KR102003420B1 (en) |
| CN (1) | CN107075279B (en) |
| AU (1) | AU2015340747A1 (en) |
| BR (1) | BR112017007551B1 (en) |
| DK (1) | DK3212719T3 (en) |
| ES (1) | ES2728127T3 (en) |
| MX (1) | MX2017005298A (en) |
| MY (1) | MY177689A (en) |
| SG (1) | SG11201703103YA (en) |
| TR (1) | TR201909251T4 (en) |
| TW (1) | TW201617418A (en) |
| WO (1) | WO2016066566A1 (en) |
| ZA (1) | ZA201702304B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112105697A (en) * | 2018-05-11 | 2020-12-18 | 中国涂料株式会社 | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, and antifouling method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG11201703104WA (en) * | 2014-10-28 | 2017-05-30 | Akzo Nobel Coatings Int Bv | A fouling control compositon comprising a polymer comprising silyl ester functional groups and quaternary ammonium/phosphonium groups |
| SG11202004174YA (en) * | 2017-12-14 | 2020-06-29 | Akzo Nobel Coatings Int Bv | Foul release coating composition, substrate coated with such coating composition, and use of such coating composition |
| CN113292921A (en) * | 2021-05-26 | 2021-08-24 | 广东电网有限责任公司 | Composite insulator coating, preparation method and spraying process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991009915A1 (en) * | 1989-12-22 | 1991-07-11 | Courtaulds Coatings (Holdings) Limited | Anti-fouling coating compositions |
| CN1832981A (en) * | 2003-07-07 | 2006-09-13 | 阿克佐诺贝尔国际涂料股份有限公司 | Silyl ester copolymer compositions |
| US20130178125A1 (en) * | 2007-11-19 | 2013-07-11 | University Of Washington | Marine coatings |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2830219B2 (en) * | 1989-11-24 | 1998-12-02 | 大日本インキ化学工業株式会社 | Resin composition for antifouling paint |
| GB9006318D0 (en) * | 1990-03-21 | 1990-05-16 | Courtaulds Coatings Ltd | Coating compositions |
| SG60054A1 (en) * | 1996-04-17 | 1999-02-22 | Nof Corp | Coating composition |
| ATE246229T1 (en) * | 1999-06-11 | 2003-08-15 | Hempels Skibsfarve Fab J C | SELF-POLISHING ANTI-GROWTH PAINT FOR WATERCRAFT - WITH SILICON CONTAINING COPOLYMERS AND FIBERS |
| ES2247136T3 (en) * | 2000-07-06 | 2006-03-01 | Akzo Nobel Coatings International B.V. | ANTI-INCRUSTATIONS PAINT. |
| KR101045922B1 (en) * | 2002-08-09 | 2011-07-01 | 아크조노벨코팅스인터내셔널비.브이. | Acid-Capped Quaternary Polymers and Compositions Comprising the Polymers |
| EP1735389A1 (en) * | 2004-02-03 | 2006-12-27 | Akzo Nobel Coatings International BV | Antifouling coating composition and its use on man made structures |
| PL1753829T3 (en) * | 2004-02-03 | 2008-07-31 | Akzo Nobel Coatings Int Bv | Antifouling compositions comprising a polymer with salt groups |
| MX2011001537A (en) * | 2008-08-13 | 2011-04-26 | Akzo Nobel Coatings Int Bv | Polymer with salt groups and antifouling coating composition comprising said polymer. |
| JP2010150355A (en) * | 2008-12-25 | 2010-07-08 | Nippon Paint Marine Kk | Anti-fouling coating composition, anti-fouling coating film, and method for controlling hydrolysis rate of anti-fouling coating film |
| EP2576472B1 (en) * | 2010-05-25 | 2016-03-23 | 3M Innovative Properties Company | Antimicrobial coatings |
| JP5916008B2 (en) * | 2010-10-14 | 2016-05-11 | 大日本塗料株式会社 | High solid content antifouling paint composition |
| EP2468825A1 (en) * | 2010-12-21 | 2012-06-27 | Akzo Nobel Coatings International B.V. | Antifouling coating composition |
| JP5632566B1 (en) * | 2013-03-15 | 2014-11-26 | 日東化成株式会社 | Antifouling paint composition and coated article having an antifouling coating film formed on the surface using the composition |
| CN105143368B (en) * | 2013-04-23 | 2017-08-04 | 中国涂料株式会社 | Antifouling paint compositions, antifouling coat, the manufacture method of antifouling base material and antifouling base material |
-
2015
- 2015-10-26 WO PCT/EP2015/074691 patent/WO2016066566A1/en active Application Filing
- 2015-10-26 ES ES15784714T patent/ES2728127T3/en active Active
- 2015-10-26 KR KR1020177013319A patent/KR102003420B1/en active IP Right Grant
- 2015-10-26 SG SG11201703103YA patent/SG11201703103YA/en unknown
- 2015-10-26 US US15/521,049 patent/US20170355861A1/en not_active Abandoned
- 2015-10-26 TR TR2019/09251T patent/TR201909251T4/en unknown
- 2015-10-26 EP EP15784714.6A patent/EP3212719B1/en active Active
- 2015-10-26 AU AU2015340747A patent/AU2015340747A1/en not_active Abandoned
- 2015-10-26 DK DK15784714.6T patent/DK3212719T3/en active
- 2015-10-26 MX MX2017005298A patent/MX2017005298A/en unknown
- 2015-10-26 JP JP2017522158A patent/JP6387187B2/en active Active
- 2015-10-26 MY MYPI2017701402A patent/MY177689A/en unknown
- 2015-10-26 BR BR112017007551-2A patent/BR112017007551B1/en active IP Right Grant
- 2015-10-26 CN CN201580057044.0A patent/CN107075279B/en active Active
- 2015-10-28 TW TW104135477A patent/TW201617418A/en unknown
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2017
- 2017-03-31 ZA ZA2017/02304A patent/ZA201702304B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991009915A1 (en) * | 1989-12-22 | 1991-07-11 | Courtaulds Coatings (Holdings) Limited | Anti-fouling coating compositions |
| CN1832981A (en) * | 2003-07-07 | 2006-09-13 | 阿克佐诺贝尔国际涂料股份有限公司 | Silyl ester copolymer compositions |
| US20130178125A1 (en) * | 2007-11-19 | 2013-07-11 | University Of Washington | Marine coatings |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112105697A (en) * | 2018-05-11 | 2020-12-18 | 中国涂料株式会社 | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, and antifouling method |
Also Published As
| Publication number | Publication date |
|---|---|
| MY177689A (en) | 2020-09-23 |
| JP2017535637A (en) | 2017-11-30 |
| ES2728127T3 (en) | 2019-10-22 |
| BR112017007551A2 (en) | 2018-02-06 |
| DK3212719T3 (en) | 2019-06-03 |
| AU2015340747A1 (en) | 2017-04-20 |
| US20170355861A1 (en) | 2017-12-14 |
| JP6387187B2 (en) | 2018-09-05 |
| TW201617418A (en) | 2016-05-16 |
| EP3212719B1 (en) | 2019-04-10 |
| TR201909251T4 (en) | 2019-07-22 |
| KR102003420B1 (en) | 2019-07-24 |
| EP3212719A1 (en) | 2017-09-06 |
| SG11201703103YA (en) | 2017-05-30 |
| MX2017005298A (en) | 2017-07-28 |
| BR112017007551B1 (en) | 2022-08-23 |
| CN107075279B (en) | 2021-07-02 |
| KR20170070204A (en) | 2017-06-21 |
| ZA201702304B (en) | 2019-06-26 |
| WO2016066566A1 (en) | 2016-05-06 |
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